JPH07172059A - Perforation transfer type recording material and recording method - Google Patents

Abstract

PURPOSE:To obtain an image recording material having high density, excellent image preservability and simple handleability by incorporating a chelate dye formable colorant in a colorant layer. CONSTITUTION:A perforation transfer type recording material comprises a colorant layer 2 and a colorant barrier layer 3 laminated on a support 1, wherein the colorant layer contains, in addition to a colorant as indispensable ingredient, binder, and the colorant is chelate formable colorant in order to obtain high sensitivity, high image preservability. As the colorant, chelate formable thermal diffusible dye is used, and durability of a dye image after transfer is improved by incorporating metal ion-containing compound to be chelate- reacted with the dye of an image receiving element in the element. The colorant is particularly preferably azo dye. The image receiving material fundamentally has a support 5 and an image receiving layer 4. The layer 4 is formed of binder for the receiving layer and various additives, and metal ion-containing compound is preferably added to the receiving layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a perforation transfer type recording material which can easily obtain an image having high density and excellent storage stability, and a recording method using the same.

[0002]

2. Description of the Related Art Conventionally, as a transfer recording method, a thermal transfer recording material having a heat-melting coloring material layer or a coloring material layer containing a heat sublimable dye provided on a substrate and an image receiving material are opposed to each other, and a thermal head is used. There is a method of transferring and recording an image by pressing a heat source controlled by an electric signal such as an energizing head from the ink sheet (recording material) side.

Further, in JP-A-63-35383 and 63-35387, a sublimable ink layer and a protective layer containing a thermoplastic resin as a main component are provided on a support, and the protective layer is a laser beam. After perforating the protective layer by melting it by making it adhere, the protective layer and the image receiving paper are brought into close contact with each other, and heating by a laser or a thermal head is applied from the side of the support having the sublimable ink layer, so that image information is thermally transferred to the image receiving layer. The technique to do is described. In this regard, Japanese Patent Laid-Open No. 4-201486 discloses
There is a disclosure regarding the technique of using a metal vapor deposition film for the dye barrier layer (corresponding to the above-mentioned protective layer).

On the other hand, US Pat. Nos. 5,156,938 and 5,171,650.
As another technique, an explosion is caused by irradiating the ink layer or a layer between the support and the ink layer with a laser beam having an extremely high power density, and this force causes the ink layer together with the binder to form an image receptor. It is described that the image is blown off and transferred.

On the other hand, in recent years, in the fields of medical treatment and printing, there has been a demand for a recording method having a high resolution, capable of recording with a high transmission density, and capable of digital recording with easy handling.
Image recording methods capable of digital recording include a sublimation type thermal transfer recording method using a thermal head, a fusion type thermal transfer recording method, a heat sensitive color recording method, an electrophotographic recording method, an inkjet recording method, etc. The transmission density was insufficient for use as an image. Further, in order to obtain excellent gradation, there is a problem that the image storability is insufficient in the sublimation type thermal transfer recording method and the thermosensitive color recording method.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides an image recording material having a high density, excellent image storability, and easy handling, a method of producing the same, and a method of recording the same. With the goal.

[0007]

The above object of the present invention is achieved by the following constitution.

(1) The coloring material barrier layer of the recording material having at least the coloring material layer and the coloring material barrier layer on the support is perforated imagewise, and the coloring material of the coloring material layer in the perforated portion is applied by heat and pressure. A perforation-transfer recording material for use in a recording method for transferring to an image-receiving layer, wherein the coloring material layer contains at least a chelate-forming coloring material.

(2) The perforation transfer recording material according to (1), wherein the colorant capable of forming a chelate dye is a compound represented by the general formula (1) [Chemical formula 1] or the general formula (2) [Chemical formula 2]. .

(3) The coloring material capable of forming a chelate dye is one selected from compounds represented by the general formula (3) [Chemical formula 3] to the general formula (12) [Chemical formula 12] (1) Perforated transfer type recording material.

(4) A perforation transfer type recording material having at least a color material layer, a color material barrier layer, an image receiving layer and a second support on a first support in this order.

(5) There is a gap of 3 to 50 μm between the color material barrier layer and the image receiving layer in a region of 90% or more of the total area.
(4) A perforated transfer type recording material.

(6) The perforation transfer recording material according to (4) or (5), wherein any one of the color material layer, the color material barrier layer and the image receiving layer contains a matting agent.

(7) The particle size of the matting agent is 5 μm or more
(6) A perforation transfer type recording material as described above.

(8) The perforation transfer recording material according to any one of (4) to (7), which has a cushion layer between the first support and the color material layer.

(9) The perforation transfer recording material according to any one of (4) to (7), which has a cushion layer between the image receiving layer and the second support.

(10) The perforation transfer recording material according to any one of (1) to (9), wherein the color material barrier layer contains an infrared absorbing dye.

(11) The coloring material barrier layer of the recording material having at least the coloring material layer and the coloring material barrier layer on the support is perforated in an imagewise manner, and the coloring material of the coloring material layer at the perforated portion is applied by heat and pressure. A recording method of transferring to an image receiving layer, wherein the color material layer contains at least a color material capable of forming a chelate, and the image receiving layer of the image receiving material contains a metal ion-containing compound.

(12) A color material barrier layer of a recording material having at least a color material layer, a color material barrier layer, an image receiving layer and a second support on the first support is imagewise perforated, and heat is applied. A perforation transfer recording method in which the color material of the color material layer in the perforated portion is transferred to the image receiving layer by pressure.

(13) A recording material having at least a color material layer and a color material barrier layer formed on a support and an image receiving material having at least an image receiving layer formed on the support are laminated under pressure (4)
A method for producing the perforated transfer recording material described.

The present invention will be described in detail below.

The perforation transfer type recording material (also simply referred to as "recording material") of the present invention basically comprises a color material layer 2 and a color material barrier layer 3 on a support 1, as shown in FIG. The layers are laminated in this order, but may have other layers if necessary. Further, in order to improve the handling property, a matting agent as shown in FIG. 2 may be contained.

The support is not particularly limited as long as it has good dimensional stability and can withstand a heat source such as a laser during image recording. For example, thin paper such as condenser paper or glassine paper; polyethylene terephthalate, polyethylene naphthalate. A heat-resistant plastic film such as polyamide, polycarbonate, polysulfone, polyvinyl alcohol, cellophane, or polystyrene can be used.

The thickness of the support is usually preferably in the range of 2 to 200 μm, more preferably 25 to 100 μm.

The color material layer contains a binder as an essential component in addition to the color material, and further contains optional components such as additives as required. In particular, in order to obtain high sensitivity and high image storability, the color material is preferably a color material capable of forming a chelate.

In the present invention, the coloring material transferred to the image receiving layer is preferably a heat diffusing dye, but not limited to this, other dyes or pigments may be used. When these are transferred, the binder component is transferred together. Alternatively, a so-called hot-melt type may be adopted.

The heat diffusing dye is not particularly limited as long as it has a heat diffusing property or a subliming property. As the heat-diffusible cyan dye, there are JP-A-59-78895, JP-A-59-227948, and JP-A-60-2496.
No. 6, No. 60-53563, No. 60-130735, No. 60-131292, No. 61-1
No. 9936, No. 61-22993, No. 61-31292, No. 61-31467,
61-35994, 61-49893, 61-148269, 62-19
Examples thereof include naphthoquinone-based, anthraquinone-based and azomethine-based dyes described in 1191, 63-91287, 63-91288, 63-290793 and the like.

As the heat-diffusible magenta dye, there is disclosed in JP-A-59
-78896, 60-30392, 60-30394, 60-253595
Issue 61-262190, Issue 63-5992, Issue 63-205288, Issue 6
4-159, anthraquinone series described in 64-63194, etc.,
Examples thereof include azo type and azomethine type dyes.

As the heat diffusible yellow dye, JP-A-59 is used.
-78896, 60-27594, 60-31560, 60-53565
No. 61-12394, No. 63-122594, etc., and methine-based, azo-based, quinophthalone-based, anthrythothiazole-based dyes and the like.

Further, it is obtained by a coupling reaction between a compound having an active methylene group of open chain type or closed type as a heat diffusible dye and an oxidized form of a p-phenylenediamine derivative or an oxidized form of a p-aminophenol derivative. Azomethine dye, phenol derivative, naphthol derivative, p-
An indoaniline dye obtained by a coupling reaction with an oxidized form of a phenylenediamine derivative or an oxidized form of a p-aminophenol derivative can also be preferably used.

The case of the perforation transfer type recording material in which the color material layer contains at least a chelate-forming color material will be described below. Such a recording material is hereinafter referred to as a "chelate material".

The color material capable of forming a chelate is a color material which becomes a chelate compound after the chelate reaction. More specifically, at least two or more ligands are present in the molecule, and 4 to 7 after the ligands are coordinated with the metal atom.
It refers to a dye precursor existing at a position where a ring structure such as a member ring can be adopted.

Examples of such a group capable of coordinating to a metal atom (also referred to as a chelatable group) include known ones. Specifically, --OH, --COOH, --NH ₂ , --NH--,- N =,
-CO-, -O-, -NHCO-, -S-, -SO-, -P =, -P
O-, -NO, -N = N- and the like.

As the dye, for example, a heat-diffusible dye capable of forming a chelate represented by the general formula (0) to the general formula (15) is used, and the image-receiving element contains a compound containing a metal ion which causes a chelate reaction with the dye. The durability of the dye image after transfer can be remarkably improved.

Examples of the colorant capable of forming a sublimable or heat diffusible chelate include hydroxyanthraquinones, hydroxynaphthoquinones, o-hydroxynitroso dyes, azomethine dyes and azo dyes. Among these, azomethine dyes, Azo dyes are preferable, and azo dyes represented by the following general formula (0) are particularly preferable.

[0036]

[Chemical 13]

In the formula, at least one ring of X ₀ is 5 to 7
Represents a group of atoms necessary for forming an aromatic carbocycle (preferably benzene) or a heterocycle composed of 4 atoms, which may form a condensed ring and which is a carbon bonded to an azo group. At least one of the adjacent positions of the atom is (a) a nitrogen atom,
Is an oxygen atom, a sulfur atom, or (b) is a carbon atom bonded to a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom,
(c) A carbon atom to which a chelatable group is bonded, and the ring may have a substituent. D represents a residue of the azo component (for example, a methine group substituted with an aromatic heterocycle).

Typical examples of the azomethine dye will be given.

[0039]

[Chemical 14]

Among the azo dyes, the dyes represented by the following general formula (1) or (2) are preferable.

[0041]

[Chemical 15]

In the formula, X ₁ and X ₂ are each an aromatic carbocycle (preferably benzene, naphthalene) or a heterocycle (for example, pyrazole, imidazole, thiazole) in which at least one ring is composed of 5 to 7 atoms. , Pyridine, benzothiazole, quinoline, pyrazoloazole, etc.) represents a group of atoms necessary for forming a condensed ring, and at least one of the adjacent positions of the carbon atoms bonded to the azo group is ( a) Is it a nitrogen atom, oxygen atom, sulfur atom,
(b) a carbon atom bonded to a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, or (c) a carbon atom bonded to a chelatable group.

[0043]

[Chemical 16]

In the formula, X ₃ has the same meaning as X ₁ and X ₂ defined in the general formula (1), and E is an electron-withdrawing group (preferably acetyl group, substituted or unsubstituted benzoyl group, cyano group or Acetamido group) and R ₁ represents an alkyl group (preferably methyl) or an aryl group (preferably phenyl).

Next, specific examples of the azo dye represented by the general formula (1) or (2) will be given.

[0046]

[Chemical 17]

[0047]

[Chemical 18]

[0048]

[Chemical 19]

[0049]

[Chemical 20]

[0050]

[Chemical 21]

[0051]

[Chemical formula 22]

[0052]

[Chemical formula 23]

[0053]

[Chemical formula 24]

Among the azo dyes represented by the general formula (1), the dyes represented by the general formulas (3) to (12) are more preferable,
In particular, the dye of the general formula (12) having a molecular weight of 330 or less is desirable in terms of high transfer sensitivity.

[0055]

[Chemical 25]

Where Z₁Is 5 with 2 carbon atoms and Q
Or a 6-membered heterocycle (eg furan, thiophene, pillow
Le, pyrazole, imidazole, triazole, pyridi
Atom, pyrazine, pyrimidine, etc.)
Represents a group, Q is -O-, -S-, -N <or -N (R)-(R
Represents a hydrogen atom or an alkyl group). R₂And R ₃
Each represents a hydrogen atom or a monovalent group, and u and w are each
It represents an integer of 1 to 5.

[0057]

[Chemical formula 26]

In the formula, L represents -CON (R ')-(R' represents an alkyl group or a hydrogen atom), -COO- or -SO _2- ,
X ₄ is a nitrogen-containing heterocycle (for example, thiazole, pyrazole, imidazole, triazole, benzotriazole, etc.) or an aromatic group in which an atom adjacent to the carbon atom to which the azo group is bonded is a nitrogen atom or a carbon atom to which a chelatable group is bonded. Represents a group carbocycle (preferably benzene), R ₄ represents an aliphatic group which may have a substituent, a heterocyclic group or a hydrogen atom, and G represents a chelatable group.

[0059]

[Chemical 27]

In the formula, R ₅ represents a group capable of substituting on the benzene ring, and n represents an integer of 0-3. When n is 2 or more, a plurality of R ₅ 's may be the same or different. R ₆ represents a hydroxyl group or an amino group.

[0061]

[Chemical 28]

In the formula, R ₇ represents a group substitutable on the benzene ring, R ₈ represents a group substitutable on the isoquinoline ring,
p and q each represent an integer of 0 to 4. When p and q are 2 or more, a plurality of R ₇ and R ₈ may be the same or different and may be bonded to each other to form a ring. R ₉ represents a hydrogen atom, a halogen atom or a monovalent substituent, and G represents a chelatable group.

[0063]

[Chemical 29]

In the formula, R ₁₀ represents an alkyl group which may have a substituent or a cycloalkyl group, and X ₅ represents ₅ together with the carbon atom bonded to the azo group and the nitrogen atom formed in the carbon atom. Or a 6-membered nitrogen-containing heterocycle (eg thiazole,
Pyridine, benzothiazole, etc.), and the heterocycle may have a substituent.
Alternatively, a 10-membered condensed ring may be formed.

[0065]

[Chemical 30]

In the formula, R ₁₁ and R ₁₂ each represent a hydrogen atom or a substituent, and X ₅ represents a carbon atom bonded to the azo group and a carbon atom bonded to the hydroxyl group together with a 6-membered nitrogen-containing compound. It represents an atomic group necessary for forming a heterocycle (preferably pyridine or quinoline), and the heterocycle may have a substituent and may further form a condensed ring.

[0067]

[Chemical 31]

In the formula, X ₇ represents an atomic group necessary for forming an aromatic carbocycle (preferably benzene or naphthalene), and X ₈ represents an atomic group necessary for forming a thiazole ring or a benzothiazole ring. , R ₁₃ represents an alkyl group.

[0069]

[Chemical 32]

In the formula, R ₁₄ represents an alkyl group, a halogen atom or a hydrogen atom, R ₁₅ represents an alkyl group or a hydrogen atom, and R ₁₆ and R ₁₇ are each an alkyl group which may have a substituent or It represents an aryl group which may have a substituent. However, at least one of R ₁₆ and R ₁₇ represents an aryl group substituted with an alkyl group or an alkyl group substituted with an alkyl-substituted aryl group.

[0071]

[Chemical 33]

In the formula, R ₁₈ and R ₁₉ each represent a hydrogen atom or a substituent, R ₂₀ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and Z ₂ is 2
Represents a group of atoms necessary to form a 5- or 6-membered heterocycle (eg, isothiazole, pyrazole, etc.) or an aromatic carbocycle (preferably benzene) together with C carbon atoms.

[0073]

[Chemical 34]

In the formula, X ₉ and X ₁₀ are each an aromatic carbocycle (preferably benzene or naphthalene) or a heterocycle (for example, thiazole, pyrazole or imidazole) in which at least one ring is composed of 5 to 7 atoms. , Triazole, pyridine, pyrazoloazole, etc.). The molecular weight of the compound is 330 or less.

Specific examples of the azo dyes represented by the general formulas (3) to (12) are shown below.

[0076]

[Chemical 35]

[0077]

[Chemical 36]

[0078]

[Chemical 37]

[0079]

[Chemical 38]

[0080]

[Chemical Formula 39]

[0081]

[Chemical 40]

[0082]

[Chemical 41]

[0083]

[Chemical 42]

[0084]

[Chemical 43]

[0085]

[Chemical 44]

[0086]

[Chemical formula 45]

[0087]

[Chemical formula 46]

[0088]

[Chemical 47]

[0089]

[Chemical 48]

[0090]

[Chemical 49]

[0091]

[Chemical 50]

[0092]

[Chemical 51]

[0093]

[Chemical 52]

[0094]

[Chemical 53]

[0095]

[Chemical 54]

[0096]

[Chemical 55]

[0097]

[Chemical 56]

[0098]

[Chemical 57]

[0099]

[Chemical 58]

[0100]

[Chemical 59]

[0101]

[Chemical 60]

[0102]

[Chemical formula 61]

[0103]

[Chemical formula 62]

Examples of azomethine dyes include the following general formulas (13) to (15).

[0105]

[Chemical formula 63]

In the formula, each of X ₁₁ and X ₁₂ has the same meaning as X ₀ defined in the general formula (0). Representative specific examples are as follows.

[0107]

[Chemical 64]

[0108]

[Chemical 65]

In the formula, X ₁₃ and X ₁₄ each have the same meaning as X ₀ defined in the above general formula (0). Representative specific examples are as follows.

[0110]

[Chemical formula 66]

[0111]

[Chemical formula 67]

In the formula, X ₁₅ and X ₁₆ each have the same meaning as X ₀ defined in the general formula (0), R ₂₁ and R ₂₂ each represent a hydrogen atom or an alkyl group, and R ₂₁ and R ₂₂ may combine to form an aromatic carbocycle. Representative specific examples are as follows.

[0113]

[Chemical 68]

The amount of these heat diffusible dyes to be used depends on the amount of Support 1
It is usually 0.1 to 20 g, preferably 0.2 to 5 g per m ² .
The content of the heat diffusible dye in the color material layer is usually 5 to 5.
It is in the range of 90% by weight, preferably 30-80% by weight.

As the binder used in the color material layer, resins known in the thermal transfer recording field can be used. The polyvinyl acetal-based resin and the cellulose-based resin described below are preferable, but not limited thereto.

As the polyvinyl acetal resin, there are various compounds depending on the degree of acetalization and the content of acetyl groups, residual hydroxyl groups and the like, and representative examples thereof include polyvinyl acetoacetal and polyvinyl butyral.

Examples of the cellulosic resin include nitrocellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose butyrate and the like. Among them, nitrocellulose is particularly preferable.

Resins known in the field of thermal transfer recording other than the above include acrylic resin, methacrylic resin, polycarbonate, polyvinyl alcohol, polyvinyl formal,
Examples thereof include polyvinyl ether, polyvinylpyrrolidone, polystyrene, polystyrene copolymers and ionomer resins.

One or more of these binders can be appropriately selected and used. The binder is
Usually, it is preferable to add 10 to 70% by weight to the entire color material layer. Further, the weight ratio of the binder and the heat diffusible dye in the color material layer is preferably in the range of 1:10 to 10: 1, and 2: 8 to
8: 2 is particularly preferred.

The thickness of the color material layer is such that it can be peeled off from the image receptor.
Moreover, it is sufficient that the dye can be moved by the application of heat energy, and it is usually in the range of 0.2 to 10 μm, preferably 0.4 to 5 μm.

The additives to be added to the coloring material layer in the present invention include modified silicone resins, fluororesins, surfactants, waxes, higher fatty acids, higher aliphatic alcohols, higher aliphatic ethers, and fine metal powders. , Silica gel, carbon black, organic fillers, inorganic fillers, curing agents that can react with binder components (for example, radiation-active compounds such as isocyanates, acrylic acid, and epoxies). Further, in order to promote transfer, a heat-melting substance such as higher fatty acid ester described in JP-A-59-106997 can be used.

The amount of the additive to be added cannot be uniformly determined depending on the kind of the additive and the purpose of addition, but the amount of the additive as a whole is preferably 50% by weight or less with respect to the binder.

Specific examples of the modified silicone resin include polyester-modified silicone resin, acrylic-modified silicone resin, urethane-modified silicone resin, cellulose-modified silicone resin, alkyd-modified silicone resin, and epoxy-modified silicone resin. They may be used alone or in combination of two or more.

The blending amount of the modified silicone resin to the coloring material layer is usually 0.01 to 10% by weight, preferably 0.01 to 2.0% by weight.

The color material layer is formed by dissolving or dispersing the above-mentioned heat diffusible dye, binder and optional additives in a solvent to prepare a coating solution, and coating and drying it on a support. be able to.

The binder may be used not only in one kind or in two or more kinds dissolved in a solvent, but also in a latex dispersion.

As the solvent, water, alcohols (eg ethanol, propanol, butanol), cellosolves, esters (eg ethyl acetate, butyl acetate), aromatics (eg toluene, xylene, chlorobenzene), ketones (eg Acetone, methyl ethyl ketone), ethers (eg tetrahydrofuran, dioxane), chlorine-based solvents (eg chloroform, trichloroethylene) and the like can be mentioned. The solvent may be used alone or in combination of two or more.

[0128] For coating, surface-sequential coating by a known gravure roll, extrusion coating, wire bar coating,
Roll coating or the like can be used.

The colorant barrier layer must have at least the property of not passing the colorant (heat diffusible dye) of the colorant layer even under heating or pressure, and the property of absorbing high-intensity exposure.
For this purpose, as a colorant barrier material, (1) a water-soluble resin, (2) a resin having an ionic bond, or (3) a Tg (glass transition point) of 80 ° C or higher, preferably 100 ° C or higher, more preferably Is preferably a resin (containing as a main component) at 120 ° C. or higher, and (4) a metal vapor deposition layer.

As the water-soluble resin, gelatin, polyvinyl alcohol, water-soluble polyvinyl formal, water-soluble polyvinyl acetal, water-soluble polyvinyl butyral, polyvinyl pyrrolidone, water-soluble polyester, water-soluble nylon, polyacrylic acid, water-soluble polyurethane, methyl cellulose, Examples thereof include hydroxypropyl cellulose. Further, copolymers of monomer components constituting these resins can also be used.

The resin having an ionic bond means a resin having an ionic bond group, that is, an acidic group or a basic group in the main chain or side chain of a polymer. The acidic group -COO ^-, -SO ₃ ^-,
PO ₃ ^{— and the} like, and basic groups include —NH ₂ , —NH
−, −N = and the like. As the resin having an ionic bond, those having both of these acidic groups and basic groups, those having an acidic group and containing a divalent metal ion, and having a cross-linking structure through this metal ion, etc. Can be mentioned.

The resin having an ionic bond of the present invention preferably has one or more of these ionic bond groups in at least 100 repeating monomer units. However, a resin which does not necessarily have a repeating monomer unit can also be used.

Examples of the resin having an ionic bond include ionomer resins and the like, styrene substituted with a sulfo group,
Resins containing acrylic acid, methacrylic acid, phthalic anhydride, etc. as copolymer components, and Na ⁺ , K as counter ions
^Examples include those to which ⁺ , Ca ²⁺ , Zn ²⁺ , NH ₄ ^+, etc. have been added. Further, gelatin, casein and the like are also preferably used.

Examples of the resin having Tg of 80 ° C. or higher include polyvinyl chloride, polyaryl methacrylate, polybenzyl methacrylate, polycarbonate, nylon, polyphenylene oxide, gelatin, polyparabanic acid and the like. Among them, polymethylmethacrylate, polybenzylmethacrylate, polycarbonate, nylon, polyester, polyparabanic acid and the like are preferable. Further, a copolymer of monomer components such as styrene, vinyl chloride, methyl methacrylate, aryl methacrylate, acrylonitrile, ethylene oxide, benzyl methacrylate, cyclohexyl methacrylate and the like having a Tg of 80 ° C. or higher is also preferably used. Further, a thermosetting resin having no glass transition point is also preferable.

The ratio of the colorant barrier material to the colorant barrier layer is preferably 50 to 99% by weight. Of all resin components of the colorant barrier layer, the ratio of the colorant barrier material is 50.
% Or more is preferable, more preferably 70% or more,
Most preferably, it is 90% by weight or more.

As the metal in the case of forming the colorant barrier layer by the metal vapor deposition layer, any metal having light absorbing property can be used, but Al, Zn, Sn, Ag, Pb, Cr, Bi, N can be used.
i, Co and the like, and oxides, hydroxides and sulfides thereof are preferable.

The colorant barrier layer may also contain a light absorbing material for absorbing high intensity exposure. The light absorbing substance may be the above resin component itself when the wavelength of high-intensity exposure is in the visible light region of ultraviolet light to 500 nm or less.

When the wavelength of high-intensity exposure is in the visible light region, various pigments and dyes that absorb the exposure wavelength can be used. When the wavelength is in the red to near-infrared region, the dyes and carbon black described in Japanese Patent Application No. 4-334584, page 7, can be used. For example, from the near-infrared absorbing dyes described in the functional materials June 1990, pp. 64-68, and the functional dyes for optical recording described in coloring materials 61 (1988) 218-223, cyanine-based dyes, squarylium System, azurenium system,
Phthalocyanine-based, naphthalocyanine-based, anthraquinone-based, dithiol metal complex salt-based, indoaniline metal complex-based, intermolecular CT complex-based, transition metal chelate-based, and aluminum diimmonium-based dyes can be selected and used.

As the infrared absorbing dye, any dye capable of absorbing infrared light having a wavelength of 700 nm or more can be used, but in order to effectively achieve the present invention, it is 700 to 120.
The molar absorption coefficient at the maximum absorption wavelength in the range of 0 nm is 50,00.
0 or more, more preferably 100,000 or more dyes are preferable.

The infrared absorbing dye used in the present invention is preferably compatible with the colorant barrier layer binder of the present invention. Furthermore, 0.1% or more in water or an organic solvent,
More preferably, it is desirable to dissolve it by 1% or more. However, those that can be mixed with the colorant barrier layer binder by dispersion are not excluded.

Another characteristic of the infrared absorbing dye of the present invention is that it can be easily decomposed by heat during laser irradiation. For example, when the temperature is raised from room temperature to 10 ° C./min in a nitrogen stream. 1% weight loss at 500 ℃
Or less, more preferably 400 ° C or less, further preferably 350 ° C
The following is preferable. However, this thermal decomposition characteristic is not essential to the present invention.

When a water-soluble resin is used as the colorant barrier material, the light-absorbing substance is also preferably water-soluble, and a tricarbocyanine dye having a water-soluble substituent such as a sulfo group is particularly preferable.

The light-absorbing substance may be added if necessary, but when the exposure wavelength is in the infrared region, it is preferable to contain 1 to 50% by weight of the above-mentioned near-infrared absorbing dye. The near-infrared absorbing dye can be added in a larger amount if it does not deteriorate the barrier function of the colorant barrier layer.

In the colorant barrier layer, other additives for improving coating properties, such as a surfactant, a conductive compound for preventing static electricity, a release agent for preventing blocking, a matting agent, etc. Can be contained as needed.

The film thickness of the color material barrier layer is preferably as thin as possible unless the barrier function is deteriorated, specifically, it is in the range of 0.01 to 2.0 μm, preferably 0.1 to 2.0 μm.
It is 1.0 μm. However, if the intensity of exposure is sufficiently high, it is possible to perforate even with a thicker film thickness, and thus the range is not limited to this range.

The color material barrier layer may be formed of a plurality of layers having separated functions as required. The functions to be separated include, for example, colorant barrier property, conductivity, light absorption,
Blocking resistance and the like can be mentioned, and these functions can be provided in different layers.

The coating of the color material barrier layer can be performed in the same manner as the color material layer.

In the present invention, a layer may be provided in addition to the color material layer and the color material barrier layer, if necessary. For example, an undercoat layer may be provided between the support and the color material layer to enhance the adhesiveness and the like. Further, a backing layer may be provided on the back surface of the support (on the side opposite to the color material layer) for the purpose of imparting running stability, heat resistance, antistatic property and the like. The thickness of this backing layer is preferably in the range of 0.1 to 1 μm.

Further, the recording material may be provided with detection marks for forming perforations or detecting the positions of areas having different hues for convenience of use.

Next, the image receiving material used together with the recording material of the present invention will be described.

The image-receiving material basically comprises a support and an image-receiving layer, but the image-receiving material can be formed by the self-supporting image-receiving layer itself.

As the support, for example, paper, coated paper, synthetic paper (polypropylene, polystyrene or a composite material obtained by laminating them on paper or a plastic film),
White or transparent polyethylene terephthalate film,
Examples thereof include white or transparent polyvinyl chloride and polyolefin-coated paper. The thickness of the support is usually 20 to 300 μm, preferably 30 to 200 μm.

The image receiving layer is formed of a binder for the image receiving layer and various additives. As the binder for the image receiving layer,
Polyvinyl chloride resin, copolymer resin of vinyl chloride and other monomers (eg alkyl vinyl ether, vinyl acetate, etc.), polyester resin, acrylic ester, polyvinylpyrrolidone, polycarbonate, cellulose triacetate, styrene acrylate resin, vinyl toluene acrylate Resin, polyurethane resin, polyamide resin, urea resin, polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin and the like can be mentioned.

The above resin may be newly synthesized and used, or a commercially available product may be used. In any case,
From the viewpoint of physical properties, Tg is -20 as a binder for the image receiving layer.
A resin in the range of to 150 ° C is preferable, and a resin in the range of 30 to 120 ° C is particularly preferable. Also, the average weight molecular weight is 2,000 to 100,000.
Resins in the range are preferred.

In the formation of the image-receiving layer, the various resins described above may be crosslinked or cured by utilizing radiation active points (if there are no reactive active points, they may be provided) by radiation, heat, moisture, a catalyst or the like. Well, in this case, a radiation-active monomer such as epoxy or acrylic, or a cross-linking agent such as isocyanate can be used.

When a chelateable dye is used in the color material layer, it is preferable to add a metal ion-containing compound to the image receiving layer.

As the metal ion-containing compound, any compound having a metal ion bonded to an organic or inorganic compound by an ionic bond or a coordinate bond can be used, but generally, an inorganic or organic metal ion is used. And salts of the organic acids are preferable, and salts and complexes of organic acids are preferable.

Examples of the above metals include I to VIII of the periodic table.
Examples include monovalent and polyvalent metals belonging to the group
Al, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Sn, Ti and Zn are preferable, and Ni, Cu, Cr, Co and Zn are particularly preferable.

Specific examples of the metal ion-containing compound include Ni
^Examples thereof include ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ and Zn ²⁺ and an aliphatic salt such as acetic acid and stearic acid or an aromatic carboxylic acid salt such as benzoic acid and salicylic acid.

Further, the complex represented by the following general formula (16) can be particularly preferably used.

General formula (16) [M (Q ₁ ) _q (Q ₂ ) _r (Q ₃ ) _s ] ^{P +} (Y ⁻ ) _{P In the} formula, M is a metal ion, preferably Ni ²⁺ , Cu ²⁺ , Cr ²⁺ ,
Represents Co ²⁺ and Zn ²⁺ . Q ₁ , Q ₂ and Q ₃ each represent a coordination compound capable of forming a coordination bond with the metal ion M, and may be the same as or different from each other.

These coordination compounds can be selected, for example, from the coordination compounds described in “Chelate Science (5)” (Nankodo).

Y represents an organic anion group, and specific examples thereof include tetraphenylboron anion and alkylbenzene sulfonate anion. q is an integer of 1 to 3, r is 0
Is an integer of ˜2, s is 0 or 1, and these are determined depending on whether the complex represented by the general formula is 4-dentate or 6-dentate, or Q ₁ , Q ₂ and Q. Determined by the number of ₃ ligands. p represents 1 or 2.

P = 0 means that the coordination compound represented by Q _{1 to} Q ₃ is an anionic compound and is electrically neutralized by the metal cation represented by M. The anionic compound is preferably a compound represented by the following general formula (17).

[0165]

[Chemical 69]

In the formula, R ₂₃ and R _{24, which} may be the same or different, each represents an alkyl group or an aryl group, and R ₂₅ represents a halogen atom, an alkyl group, an alkoxy group or an alkoxycarbonyl group.

Anionic compound (X ⁻ ) of formula (17)
Specific examples of the metal ion-containing compound M ²⁺ (X ⁻ ) ₂ formed from the metal ion (M ²⁺ ) and the metal ion (M ²⁺ ) are shown below, but the invention is not limited thereto.

[0168]

[Chemical 70]

The amount of the metal ion-containing compound added is preferably 0.5 to 20 g, and more preferably 1 to 15 g, per m ² of the image receiving material. In other words, it is contained in an amount of 1.5 mol or more, more preferably 3 mol or more, per 1 m ^{2 of the} chelating dye contained in the color material layer per 1 m ² .

A peeling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler (filler) and a pigment can be added to the image receiving layer. Moreover, you may add a plasticizer, a thermal solvent, etc. as a sensitizer.

The image-receiving layer may be prepared by dispersing or dissolving the components for forming the image-receiving layer in a solvent to prepare a coating solution, coating on the surface of a support and drying the mixture, or a mixture containing the components for forming the image-receiving layer. It can be formed by a laminating method in which the surface of the melt-extruded support is laminated.

The image receiving layer may be formed on the entire surface of the support or may be formed on a part of the surface.

The thickness of the image receiving layer is generally 1 to 50 μm, preferably about 2 to 10 μm. On the other hand, when the self-supporting image-receiving layer itself forms the image-receiving material, the thickness of the image-receiving layer is usually 60 to 200 μm, preferably about 90 to 150 μm.

An overcoat layer may be laminated on the surface of the image receiving material for the purpose of preventing fusion and improving image storability. The overcoat layer can be formed by gravure coating, wire bar coating, roll coating, or any other known coating method or laminating method. The thickness of this layer is usually 0.05 to 3 μm.

When the image receiving material comprises a support and an image receiving layer, a cushion layer is provided between the support and the image receiving layer in order to reduce noise and transfer and record an image corresponding to image information with good reproducibility. Can be provided.

The cushion layer is made of urethane resin, acrylic resin, ethylene resin, ethylene
-Vinyl acetate resin, epoxy resin, styrene-butadiene resin,
Butadiene rubber and the like can be mentioned. The thickness of the cushion layer is preferably 5 to 25 μm.

Next, a perforation transfer type recording material having a color material layer, a color material barrier layer, an image receiving layer and a second support on at least a first support as shown in FIG. 2 will be described.
The recording material is hereinafter referred to as "integrated material".

A color material layer of an integrated material, a color material barrier layer,
The image-receiving layer and the support can have the same structure as that of the chelate-type material except for the following.

The method for producing the integrated material is not particularly limited, but the following method can be used.

(1) A method in which a color material layer, a color material barrier layer, an image receiving layer, and a second support layer are sequentially provided on the first support by coating.

(2) A method in which a color material layer and a color material barrier layer are provided on the first support by coating, and an image receiving layer is separately provided on the second support, and the two are bonded together under pressure.

Among the methods (1) and (2), the method (2) is preferable. Regarding the method of (2), other combinations can be adopted depending on which layer is applied to which support and then the layers are attached.
The combination shown in (2) is most preferable.

When laminating, a method of passing between two pressure rolls, a method of pressure bonding with a flat plate press and the like are used. The laminating pressure is preferably 0.1 to 5 kg / cm ² . In particular, when the space between the color material barrier layer and the image receiving layer is 3 to 50 μm in the area of 90% or more of the total area, the two supports should be bonded together with the weakest pressure possible as long as they can be integrated. Is preferred.

In order to integrate the two supports, an adhesive layer is further applied onto the uppermost layer (eg, colorant barrier layer, image receiving layer) of either or both of the respective supports, and then the layers are laminated. May be. The adhesive layer may be applied to the entire surface as long as the characteristics of the recording material are not impaired, but it is preferable to apply only to the peripheral portion of the material so as not to affect the image recording portion.

In the perforation transfer type recording method of the present invention,
Since the colorant barrier layer is removed by explosion or burning by high-intensity exposure, it is preferable that one side of the colorant barrier layer is opened as a space. In order to obtain this space, it is necessary for the integrated material to have a minute gap between the colorant barrier layer and the image receiving layer. The interval is preferably 3 to 50 μm, more preferably 5 to 25 μm.

Various methods can be used for forming the gap, but spacer beads can be added by adding them to the color material layer, the color material barrier layer, the image receiving layer or other layers provided as necessary. In particular, it is preferably added to the color material layer or the image receiving layer.

The material of the spacer beads is not particularly limited, but silica, silicon particles, acrylic resin polymer, styrene resin polymer, Teflon fine particles and the like can be used. The particle size of the beads may be a particle size that can achieve the above-mentioned interval, but since a part is embedded in the layer, a particle size slightly larger than the required interval is good, preferably 5-100.
μm, more preferably 10 to 50 μm.

The addition amount of the beads depends on the film thickness of the layer to be added, the particle size of the beads, and the necessary interval, and therefore cannot be specified unconditionally, but it is 0.1-10% by weight of the binder weight of the layer to be added.
Is a guide.

Next, the thermal transfer recording method (image formation) of the present invention will be described.

In the image forming process, as shown in FIGS. 1 and 2, first, high-strength exposure is performed from the color material barrier layer side of the recording material, so that the color material barrier layer is imagewise perforated. And a step of superposing the perforated recording material and the image receiving material so that the colorant barrier layer and the image receiving layer face each other, and then heating and / or pressing the entire surface.

The exposure means will be described in more detail. As a light source for this high intensity exposure, it is easy to focus with an optical system,
It is preferable that light with a large output energy and a wavelength that is easily converted into heat can be emitted. As such a light source,
For example, xenon light, halogen light, semiconductor laser, L
ED, helium neon laser, argon laser, Y
Examples thereof include AG laser and carbon dioxide gas laser.
Among these, examples of light sources that are easy to use as an array composed of a plurality of light emitting elements include semiconductor lasers and LEDs.

The light emitting element is preferably one capable of emitting light having a wavelength capable of efficiently converting exposure energy into heat energy, and a preferable emission wavelength is, for example,
It is 600 to 2000 nm.

When a semiconductor laser is used, an automatic output control (APC) method or an automatic current control (ACC) method can be adopted as a light source driving method. In any case, it is preferable to provide a protection circuit for preventing the semiconductor laser from being destroyed by a temporary excessive current.

A plurality of light sources may be arranged in parallel as required. In this case, the exposure system is preferably arranged so that a plurality of light sources scan different scanning lines, and the number of channels of the light sources is preferably 1 to 100.

FIG. 3 and FIG. 4 show an embodiment of the arrangement of the light emitting elements as the heat mode recording light source. In FIG. 3, a total of 16 light emitting elements arranged in parallel are used. In FIG. 4, the light-emitting element array is likewise made up of a total of 16 light-emitting elements in groups of 6, 6, and 4 and arranged at a predetermined angle θ, and the light-emitting elements are, for example, semiconductor lasers with the same rated output of 100 mW. Is used.

The exposure spot diameter of each light emitting element of this light emitting element array is basically determined by the required image resolution. For example, a spot diameter of 1 / e ² is 3 to
The range of 40 μm is preferred. The light emitting element has a size of, for example, 1 mm or more, whereas the spot diameter is, for example, 3 to 40 μm in the exposed portion, so that the exposure direction is not bent toward the inner side as the outer light emitting element is. must not. However, if the exposure direction is bent too much,
It is not preferable because the spot diameter is distorted. In order to reduce as much as possible the restriction of the arrangement of the light emitting elements as an array, it is preferable to arrange the light emitting elements in the array as shown in FIG.

In such laser perforation recording,
By shortening the exposure time, energy loss due to heat conduction from the color material barrier layer to the color material layer side of the recording material is reduced. Compared with normal thermal transfer recording in which the ink layer is heated by thermal conduction from the support side using a thermal head,
In laser perforation recording, thermal energy is directly applied in the vicinity of the color material barrier layer.

Therefore, it is preferable that the exposure is performed with high illuminance and in a short time as much as possible. A preferable exposure speed is a linear velocity of 1 m / sec or more, more preferably 3 m / sec or more. Further, the preferable exposure power density is 100,000 W / cm ² or more, more preferably 200,000 W / cm ² or more.

As a semiconductor laser scanning method, a polygon mirror or galvano mirror and an fθ lens are combined to perform main scanning of laser light, and sub-scanning is performed by moving a recording medium. There is a cylindrical scan in which the laser exposure is performed while performing the main scanning while the drum rotation is the main scanning and the laser light movement is the sub-scanning. However, the cylindrical scanning is easier to enhance the accuracy of the optical system and is suitable for high density recording. There is.

In order to make full use of the characteristics of laser perforation recording, it is preferable that the dot pitch is finer than that of a general thermal head, and 2.5 to 25.4 μm, more preferably 3 to
It is 12.7 μm. Further, it is preferable that the dot pitches in the main scanning direction and the sub scanning direction match.

Any method can be used for the image signal processing method shown here. Further, the base image data may be an analog signal or a digital signal.

The holes formed by high-intensity exposure may be halftone dots or continuous holes.

The heat energy can be applied from the image receiving material side, the recording material side, or both when superposing the recording material and the image receiving material and heating the entire surface. By this heating, the heat diffusible dye of the color material layer diffuses and transfers from the color material layer to the image receiving layer of the image receiving material through the holes of the color material barrier layer to form an image. The heating temperature and pressure are not particularly limited, but the heating temperature is usually preferably in the range of 60 to 200 ° C, more preferably 80 to 150 ° C, and the pressure is preferably 0.1 to 5 kg / cm ² .

In this case, the image is formed corresponding to the shape of the holes of the color material barrier layer, and becomes an image or a solid image. In the case of halftone dots, the image density increases as the number of halftone dots increases (the image density increases according to the number of holes).

Since the recording material of the present invention has the colorant barrier layer formed on the colorant layer, it has excellent storability.

Further, in the thermal transfer recording method of the present invention, high resolution recording is carried out by using a laser beam for perforating the color material barrier layer, and each recording dot is further provided with a gradation to obtain an area scale. Tone and density gradation are combined to express the gradation of light and shade of the image in a very wide range, and the high density of heat or pressure promotes the diffusion of the dye to the image receiving material, thus making the density of the image extremely high. Can be increased.

[0207]

EXAMPLES The present invention will be described in more detail based on the following examples, but the embodiments of the present invention are not limited thereto.
In the following, "part" means "part by weight".

Example 1 (Production of Recording Material) The following composition was mixed and dispersed to prepare a coating material for a color material layer containing a heat diffusible dye.

Color material layer coating solution Chelate-type heat-diffusible dye (the following) 40 parts Polyvinyl butyral resin (Sekisui Chemical Co., Ltd .: S-REC BX-1) 60 parts Methyl ethyl ketone 700 parts Cyclohexanone 200 parts 1,2-7,3
-2,4-13,5-1,6-1,7-1,8-1,9-
7, 9-10, 10-1, 11-24, 11-26, 12-1, 12-2
4, 12-38 were used respectively.

The color material layer coating solution was applied onto a polyethylene terephthalate (PET) film having a thickness of 100 μm using a wire bar and dried to form a color material layer having a thickness of 4 μm.

Next, a coloring material barrier layer coating solution having the following formulation is applied onto the above coloring material layer using a wire bar and dried to form a coloring material barrier layer having a thickness of 0.15 μm to obtain a recording material. It was

Color material barrier layer coating solution Gelatin 3.0 parts Near infrared absorbing dye (IR-1) 2.0 parts Pure water 95 parts

[0213]

[Chemical 71]

(Manufacture of Image Receiving Material) An image receiving layer coating solution having the following composition was formed on the surface opposite to the antistatic processed surface of 100 μm-thick PET having a surface resistance of 10 ¹⁰ Ω and antistatic processing applied to the back surface. Was applied using a wire bar and dried at 120 ° C. for 30 minutes to form an image receiving layer having a thickness of 4 μm.

Image receiving layer coating solution Polyvinyl butyral (Sekisui Chemical Co., Ltd .: S-REC BL-1) 40 parts Metal ion-containing compound (17-4) 50 parts Amino-modified silicone (Shin-Etsu Silicon Co., Ltd .: KF-393) 5 parts Epoxy-modified Silicon (X-22-343 manufactured by Shin-Etsu Silicon Co., Ltd.) 5 parts Methyl ethyl ketone 300 parts Cyclohexane 100 parts (image formation) << Perforation of colorant barrier layer >> Semiconductor laser SDL-8032-on the colorant barrier layer of the recording material. A laser beam of 101 (manufactured by Sanyo Electric Co., Ltd .: wavelength: 810 nm, maximum light output: 150 mW) was condensed, and exposure was performed with a beam diameter having a half width at maximum output of 5 μm. The laser exposure device was arranged as shown in FIG. 4, and exposure was performed using 16 semiconductor lasers.

The light output on the focal plane at the time of exposure was 101 mW on average per semiconductor laser. Also, the exposure energy density during solid exposure calculated from the scanning speed of exposure is
It was 150 mJ / cm ² .

<< Transfer of Coloring Material >> As described above, the coloring material barrier layer of the recording material in which the coloring material barrier layer is perforated and the image receiving layer of the image receiving material are superposed so as to be in contact with each other, and 160 ° C. × 2 kg / cm ²
Then, the coloring material was transferred to the image receiving layer through the perforated portion.

The characteristics of each of the obtained images were evaluated by the following evaluation methods. The results obtained are shown in Table 1.

<Sensitized Density of Solid Exposure Area and Unexposed Area> Using a Sakura Densitometer PDA65 (manufactured by Konica Corporation), the transmission density of each image was adjusted according to the color tone of each dye through blue, green and red filters. It was measured. Incidentally, the transmission density of the unexposed portion showed the same value as 0.04 for all the images, and therefore it was omitted in Table 1.

<Fixability> The surface of the image receiving layer of each obtained image and the coating surface of a sheet obtained by coating a nitrocellulose layer having a thickness of 5 μm on a PET film having a thickness of 180 μm are superposed at 140 ° C. After heating for 2 minutes, the degree of transfer of the dye from the image-receiving layer to the nitrocellulose layer was visually evaluated in three levels. The less the retransfer of the dye, the better the fixability.

◯: Retransfer is not observed. Δ: Retransfer is slightly observed. X: Retransfer is remarkable. <Light resistance> Each image is irradiated with a xenon fade meter for 72 hours, and the density before irradiation is changed. When D _{0 is} the concentration after irradiation and D is the concentration after irradiation, the light resistance was evaluated using (D / D ₀ ) × 100 (%) as the residual ratio of the dye.

<Bleed> A line-and-space pattern image having a line width of 20 μm was prepared using each recording material and stored at 50 ° C. for one month, and then the image was visually observed using a microscope. Bleeding was evaluated.

B: Almost no bleeding is observed B: Line and space density difference can be confirmed X: Line and space cannot be confirmed

[0224]

[Table 1]

As is clear from the table, by incorporating a chelate-forming coloring material into the perforation transfer type recording material,
The light resistance is 80% or more, the fixing property and the bleeding are also good. Especially, the dyes represented by the general formulas (9) to (11) have the light resistance, and the dyes of the general formula (12) have an excellent maximum density. It was

Example 2 (Production of Recording Material) The following compositions were mixed and dispersed to prepare a coating material for a coloring material layer containing a heat diffusible dye.

Color material layer coating solution Chelate type heat diffusible dye (D-1) 25 parts 〃 (D-2) 15 parts 〃 (D-3) 40 parts Polyvinyl butyral resin (S-REC BX-1: supra) 20 Part Methyl ethyl ketone 700 parts Cyclohexanone 200 parts The above color material layer coating solution was applied onto a PET film having a thickness of 100 μm using a wire bar and dried to form a color material layer having a thickness of 4 μm.

Next, a coloring material barrier layer coating solution having the following formulation is applied onto the above coloring material layer using a wire bar and dried to form a coloring material barrier layer having a thickness of 0.15 μm to obtain a recording material. It was

Color material Barrier layer coating solution Gelatin 2.5 parts Near infrared absorbing dye (IR-2) 2.0 parts Colloidal silver 0.5 parts Pure water 95 parts

[0230]

[Chemical 72]

(Production of Image Receiving Material) An image receiving material was prepared in exactly the same manner as in Example 1.

(Formation of Image) << Perforation of Coloring Material Barrier Layer >> Laser exposure was performed in the same manner as in Example 1 to perforate the coloring material barrier layer.

<< Transfer of Color Material >> As described above, the color material barrier layer of the recording material in which the color material barrier layer is perforated and the image receiving layer of the image receiving material are superposed so as to be in contact with each other, and 180 ° C. · 2 kg / cm ²
Then, the coloring material was transferred to the image receiving layer through the perforated portion.

The PET film transmission density was 0.02, the unexposed area transmission density was 0.04, and the solid exposure area transmission density was 3.28.
Furthermore, in order to confirm the storability of the obtained image, the image was stored at 50 ° C. for 1 month, but even when compared with a reference stored at room temperature, the image did not bleed and showed good storability.

Example 3 (Production of Recording Material) The following composition was mixed and dispersed to prepare a coloring material layer coating solution containing a heat diffusible dye.

Color material layer coating liquid Thermal diffusible dye (Nippon Kayaku Co., Ltd .: Kayaset Blue 714) 4 parts Polyvinyl butyral resin (ESREC BX-1: mentioned above) 4 parts Methyl ethyl ketone 90 parts Cyclohexanone 10 parts The above color material layers The coating liquid was applied onto a PET film having a thickness of 100 μm using a wire bar and dried to form a color material layer having a thickness of 4 μm. A nitrocellulose layer containing a silicon-modified urethane resin (Dainichi Seika: SP-2105) was provided as a backing layer on the back surface of the PET film.

Next, a coloring material barrier layer coating solution having the following formulation was applied onto the above coloring material layer using a wire bar and dried to form a coloring material barrier layer having a thickness of 0.5 μm to obtain a recording material. .

Color Material Barrier Layer Coating Solution Gelatin 3.5 parts Near infrared absorbing dye (IR-1) 1.5 parts Pure water 95 parts (Production of image receiving material) Synthetic paper with a thickness of 150 μm (Oji Yuka Synthetic Paper Co., Ltd .: YUPO FPG-150) is coated with an image receiving layer coating solution having the following composition using a wire bar, and then temporarily dried by a dryer, and then dried in an oven at 100 ° C for 1 hour to form an image receiving layer having a thickness of 5 µm on synthetic paper. An image receiving material having the above was obtained.

Image- Receiving Layer Coating Solution Vinyl Chloride-Vinyl Isobutyl Ether Copolymer 8.5 parts (BASF Corporation: Laroflex MP25) Polymethylmethacrylate spherical fine particles (particle size 12 to 15 μm) 0.5 part Polyester-modified silicone resin 1 part (Shin-Etsu Silicone Mfg .: X-24-8300) Methyl ethyl ketone 40 parts Cyclohexanone 10 parts 1 kg / cm ^{2 of} the recording material and the image receiving material prepared as described above.
-Integrated by passing through a 90 ° C hot roll.

(Formation of Image) << Perforation of Color Material Barrier Layer >> A laser beam of a semiconductor laser LTO90MD / MF (manufactured by Sharp: wavelength 830 nm, maximum light output 100 mW) is condensed on the color material barrier layer of the recording material. Then, a beam having a diameter of about 6 μm was produced at the maximum output, and the colorant barrier layer was perforated by irradiation with a scanning pitch of 10 μm and a scanning speed of 2 m / sec (optical efficiency was 60%).

<< Transfer of Coloring Material >> The integrated material in which the colorant barrier layer is perforated is passed through a heat roll capable of heating and pressing at 3 kg / cm ² at 130 ° C., and only the perforated portion is colored with a coloring material (diffusible dye). ) Was transferred to the image receiving layer.

The obtained image had no transfer omission due to foreign matter, and the red reflection density (solid density) of the solid transfer portion composed of dots of 8 μm diameter was measured and found to be 3.1. The reflection density (white background density) of the non-perforated portion was 0.06, which was the same as the reflection density of the image receiving material before passing through the heat roll.

Example 4 In the same manner as in Example 2, a recording material was prepared by changing the formulation of the coating solution for the color material layer on PET having a thickness of 12 μm as follows, and then the following image receiving material was prepared.

Color material layer coating solution Chelate type heat diffusible dye (Exemplified compound 11-26) 22 parts (Exemplified compound 10-1) 13 parts (Exemplified compound 9-7) 35 parts Matting agent (average particle size 17 μm , Soken Chemical Co., Ltd .: MR-20G) 10 parts Polyvinyl butyral resin (S-REC BX-1: aforesaid) 20 parts Methyl ethyl ketone 700 parts Cyclohexanone 200 parts (manufacture of image-receiving material) The back surface is subjected to antistatic treatment and surface resistance is 5 A 175 μm-thick PET film with a thickness of × 10 ⁹ Ω was applied to the surface opposite to the antistatic processed surface using a doctor blade to give a dry film thickness of 10 μm.
The cushion layer is provided.

Cushion layer coating liquid Ethylene-vinyl acetate resin 30 parts (Mitsui DuPont Polychemical Co., Ltd .: EVAflex EV-40Y) Toluene 60 parts Methyl ethyl ketone 10 parts Next, a silicone surface treating agent was used to impart releasability. The coating solution for the image receiving layer having the following formulation is applied to the 25 μm-thick PET surface-treating agent coated surface with a wire bar to give a dry film thickness of 3
A μm image-receiving layer was formed.

Image receiving layer coating liquid Vinyl chloride resin (Shin-Etsu Chemical Co., Ltd .: TK-300) 40 parts Metal ion-containing compound (17-4) 50 parts Amino-modified silicone (KF-393: supra) 5 parts Epoxy-modified silicone 5 Part (Shin-Etsu Silicon Co., Ltd .: X-22-343) Methyl ethyl ketone 300 parts Cyclohexanone 100 parts The image receiving layer surface provided on the 25 μm releasable PET and the cushion layer surface of 175 μm PET coated with the cushion layer prepared above are faced to each other. Then, pressurize at 3kg / cm ² with a laminator at room temperature, attach the two sheets together, and then peel off the releasable PET.
An image receiving material having a cushion layer and an image receiving layer formed on T in this order was obtained.

(Integration processing) Next, the barrier layer surface of the recording material and the image receiving layer surface of the image receiving material are opposed to each other, and a pressure of 0.5 kg / cm ² is applied by a laminator at room temperature to integrate the recording material and the image receiving material. I went.

(Formation of image) The color material barrier layer was perforated in the same manner as in Example 1, and the integrated material was heated and pressed at 180 ° C. for 5 kg through a laminator, and then separated. . The film transmission density was 0.04, and the non-exposed area transmission density and the solid exposure area transmission density were 0.04 and 3.58, respectively.

Due to the integration, the transfer omission due to the adhesion of foreign matter at the time of image formation was eliminated. The obtained image was excellent in fine line reproducibility and had a more uniform line width than the image obtained in Example 2.

[0250]

EFFECTS OF THE INVENTION The perforated transfer type recording material of the present invention which is easy to handle and the recording method using the same can stably provide a dye image having a high density and excellent image storability.

[Brief description of drawings]

FIG. 1 is a time-series schematic view of a step of performing a recording method of the present invention using a recording material of the present invention.

FIG. 2 is a time-series schematic view of a step of carrying out the recording method of the present invention by using a recording material of another constitution of the present invention.

FIG. 3 is a layout example of light emitting elements of a light source used in the present invention.

FIG. 4 is another arrangement example of the light emitting elements of the light source used in the present invention.

[Explanation of symbols]

 1 Recording Material Support 2,12 Coloring Material Layer 3,13 Coloring Material Barrier Layer 4,14 Image Receiving Layer 5 Image Receiving Material Support 11 First Support of Integrated Material 15 Second Support of Integrated Material 16 Mat Agent 17 Transferred color material

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yamato Komamura Konica Stock Company, 1 Sakura-cho, Hino-shi, Tokyo In-house

Claims (13)

[Claims] 1. A color material barrier layer of a recording material having at least a color material layer and a color material barrier layer on a support is image-wise perforated, and the color material of the color material layer in the perforated portion is received by heat and pressure. A perforation-transfer recording material for use in a recording method for transferring to a layer, wherein the coloring material layer contains at least a coloring material capable of forming a chelate dye. 2. The perforation transfer recording material according to claim 1, wherein the coloring material capable of forming a chelate dye is a compound represented by the following general formula (1) or general formula (2). [Chemical 1] [In the formula, each of X ₁ and X ₂ has at least one ring of 5 to 5;
It represents an atomic group necessary for forming an aromatic carbocycle or a heterocycle composed of 7 atoms, and may form a condensed ring, and at least one of the adjacent positions of the carbon atoms bonded to the azo group. Is a (a) nitrogen atom, oxygen atom, or sulfur atom,
(b) a carbon atom bonded to a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, or (c) a carbon atom bonded to a chelatable group. ] [Chemical 2] [In the formula, X ₃ has the same meaning as X ₁ and X ₂ defined in the general formula (1), E represents an electron-withdrawing group, and R ₁ represents an alkyl group or an aryl group. ] 3. The perforation transfer according to claim 1, wherein the colorant capable of forming a chelate dye is one selected from compounds represented by the following general formulas (3) to (12). Mold recording material. [Chemical 3] [In the formula, Z ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring with 2 carbon atoms and Q, and Q is -O-,
-S-, -N <or -N (R)-(R represents a hydrogen atom or an alkyl group) is represented. R ₂ and R ₃ are each a hydrogen atom or 1
Represents a valent group, and u and w each represent an integer of 1 to 5. ] [Chemical 4] Wherein, L is -CON (R ') - (represents a R' is an alkyl group or a hydrogen atom), - COO- or -SO ₂ - represents, X ₄ is adjacent to the carbon atom bonded to the azo group Wherein the atom represents a nitrogen atom or a nitrogen-containing heterocycle or aromatic carbocycle which is a carbon atom to which a chelatable group is bonded, and R ₄ is an aliphatic group, heterocyclic group or hydrogen atom which may have a substituent. Represents ] [Chemical 5] [In the formula, R ₅ represents a group capable of substituting on the benzene ring, and n represents an integer of 0 to 3. When n is 2 or more, a plurality of R ₅ 's may be the same or different. R ₆ represents a hydroxyl group or an amino group. ] [Chemical 6] [In the formula, R ₇ represents a group capable of substituting for a benzene ring, R ₈ represents a group capable of substituting for an isoquinoline ring, and p and q each represent 0.
Represents an integer of 4; When p and q are 2 or more, a plurality of R ₇ ,
R _{8 s} may be the same or different and may be bonded to each other to form a ring. R ₉ represents a hydrogen atom, a halogen atom or a monovalent substituent, and G represents a chelatable group. ] [Chemical 7] [In the formula, R ₁₀ represents an alkyl group or a cycloalkyl group which may have a substituent, and X ₅ represents 5 or 6 together with the carbon atom bonded to the azo group and the nitrogen atom bonded to the carbon atom. Represents a group of atoms necessary for forming a 5-membered nitrogen-containing heterocycle, and the heterocycle may have a substituent and may form a 9- or 10-membered condensed ring. ] [Chemical 8] [In the formula, R ₁₁ and R ₁₂ each represent a hydrogen atom or a substituent, and X ₆ represents a 6-membered nitrogen-containing heterocyclic ring together with the carbon atom bonded to the azo group and the carbon atom bonded to the hydroxyl group. Represents a group of atoms necessary for forming a heterocycle, which may have a substituent, and may further form a condensed ring. ] [Chemical 9] [In the formula, X ₇ represents an atom group necessary for forming an aromatic carbocycle, X ₈ represents an atom group necessary for forming a thiazole ring or a benzothiazole ring, and R ₁₃ represents an alkyl group. ] [Chemical 10] [In the formula, R ₁₄ represents an alkyl group, a halogen atom or a hydrogen atom, R ₁₅ represents an alkyl group or a hydrogen atom, and R ₁₆ and R ₁₇ each represent an alkyl group or a substituent which may have a substituent. Represents an aryl group which may have. However, at least one of R ₁₆ and R ₁₇ represents an aryl group substituted with an alkyl group or an alkyl group substituted with an alkyl-substituted aryl group. ] [Chemical 11] [Wherein, R ₁₈ and R ₁₉ each represent a hydrogen atom or a substituent, R ₂₀ represents an alkyl group which may have a substituent or an aryl group which may have a substituent, and Z ₂ represents Represents the group of atoms necessary to form a 5- or 6-membered aromatic carbocycle or heterocycle with 2 carbon atoms. ] [Chemical formula 12] [In the formula, each of X ₉ and X ₁₀ has at least one ring of 5
It represents a group of atoms necessary to form an aromatic carbocycle or a heterocycle composed of 7 atoms and may form a condensed ring. The molecular weight of the compound is 330 or less. ] 4. A perforation transfer type recording material comprising at least a color material layer, a color material barrier layer, an image receiving layer and a second support in this order on a first support. 5. The perforation transfer recording material according to claim 4, wherein a gap between the colorant barrier layer and the image receiving layer is 3 to 50 μm in a region of 90% or more of the total area. 6. The color material layer, the color material barrier layer or the image receiving layer contains a matting agent.
Alternatively, the perforation transfer type recording material according to item 5. 7. The perforation transfer type recording material according to claim 6, wherein the matting agent has a particle size of 5 μm or more. 8. The perforated transfer type recording material according to claim 4, further comprising a cushion layer between the first support and the color material layer. 9. The perforation transfer recording material according to claim 4, further comprising a cushion layer between the image receiving layer and the second support. 10. The perforation transfer recording material according to claim 1, wherein the color material barrier layer contains an infrared absorbing dye. 11. A color material barrier layer of a recording material having at least a color material layer and a color material barrier layer on a support is imagewise perforated, and the color material of the color material layer at the perforated portion is received by heat and pressure. A recording method of transferring to a layer, wherein the color material layer contains at least a chelate-forming color material, and the image receiving layer of the image receiving material contains a metal ion-containing compound. 12. A color material barrier layer of a recording material having at least a color material layer, a color material barrier layer, an image receiving layer, and a second support on a first support in this order, imagewise perforated, and heat and pressure are applied. A perforation transfer type recording method, characterized in that the coloring material of the coloring material layer at the perforated portion is transferred to the image receiving layer. 13. A recording material having at least a coloring material layer and a coloring material barrier layer formed on a support, and an image receiving material having at least an image receiving layer formed on the support are bonded together under pressure. 4. The method for producing a perforation transfer recording material according to 4.